JPS6151070B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a treatment agent for making wool shrink-proof. It is known that untreated wool shrinks in the washing solution and becomes felt during washing. To counteract this shrinkage and felting, chemical treatments have already been recommended that either change the structure of the wool or use finishes containing resins that settle on the surface of the wool fibers and coat this surface. It's here.
However, both methods result in products whose so-called feel is unpleasant to those skilled in the art. It has also already been recommended to reduce the shrinkage of wool during washing by treatment with organosilicon compounds. This type of method is described in British Patent No. 594901,
It is reported in the specifications of the same No. 61327 and the same No. 629329. According to these methods, wool is treated with a certain silane. GB 746307 describes a method for preventing shrinkage of wool, in which wool fibers are finished with certain organopolysiloxanes. Although a certain degree of shrink resistance is indeed achieved by this, this effect is not washfast. A series of other documents, for example West German Patent Application Nos. 2242297, 2335751 and 2523270
The publication describes a method for making keratin fibers shrink-proof by applying an organopolysiloxane, the distinguishing feature of which is that this compound contains amino groups. . For example, the method according to West German Patent Application No. 2242297 is characterized in that an organopolysiloxane having units of the general formula: R ⁵ _o SiO〓〓 is used,
In this case, n has an average value of 1.9 to 2.1, R ⁵ is an organic group bonded to silicon via a silicon-carbon bond, and R ⁵ is an organic group bonded to silicon via a silicon-carbon bond. represents a group, where the substituent R ⁵ is 0.25 to 50
% includes at least one imino group and at least one primary or secondary amino group -NX ₂ (where X
is a hydrogen atom, an alkyl group or an aryl group having 1 to 30 carbon atoms), is a monovalent group having less than 30 carbon atoms, and the remaining substituent R ⁵ is a monovalent group. hydrovalent radicals, halogenated hydrocarbon radicals, carboxyalkyl radicals or cyanalkyl radicals having 1 to 30 carbon atoms, at least 70% of which consist of monovalent hydrocarbon radicals having 1 to 18 carbon atoms; be. From DE 23 35 751 A1 a method for treating keratin fibers is known, characterized in that the organopolysiloxane composition contains a product obtained by mixing A) and B). and in this case A is a polydiorganosiloxane having an unterminated hydroxy group bonded to a silicon atom and a molecular weight of at least 750 (in this case, at least 50% of the organic substituents of the polydiorganosiloxane are methyl groups, and the other substituents are 1 with 2 to 30 carbon atoms
valent hydrocarbon group ₎ , and B has the general formula ^: R ⁶ SiR ⁷ _o represents a monovalent group having at least two amino groups and bonded to a silicon atom via a silicon-carbon bond, R ⁷ represents an alkyl group or an aryl group, and X represents 1- represents an alkoxy group having 4 carbon atoms, n represents 0 or 1] and/or partial hydrolyzates and condensates of organosilanes. It is reported in this West German patent application that if a coating is to be obtained from an aqueous medium, both mixture components should be reacted. However, practical experiments have taught that it is not possible to produce stable aqueous emulsions from reaction products of this type. A gel-like reaction product is formed which cannot be converted into emulsion form. The products are therefore not suitable for shrink-proofing wool from the aqueous phase. If this reaction product is used in the form of an organic solvent, it is clear that the effects that can be extracted relative to the effective amounts used are too small in practice. Furthermore, the siloxane gels that clog the wool processing equipment are separated from the solvent-containing cleaning liquid after a few hours by the action of air moisture. Furthermore, a process for the treatment of textile materials, for example wool, is known from DE 176 9 249, in which organosiloxanes containing mercaptopropyl groups are used in the form of emulsions. However, with this compound it is only possible to reduce the fouling properties. This compound is not suitable for making wool shrink-proof. Furthermore, a hair treatment agent based on an organosilicon compound is known from West German Patent Application No. 1617443, which has the general formula: [wherein R ⁸ represents an alkyl group having at least 8 C atoms, R ⁹ represents a lower alkyl group having 1 to 7 C atoms, n is an integer of at least 2, p is 0, 1 or 2, m is 0, 1 or 2, m is the sum of p has a value of 0 to 2, x is an integer at least 1, y and z
are each 0 or an integer, in which case if y is 0 then p is at least 1, if z is 0 then m is at least 1, and x is greater than the sum of y and z]. It is characterized by containing coalescence. This compound is also not suitable for making wool shrink-proof. From these above-mentioned documents, it was not possible to infer what kind of composition an organopolysiloxane suitable for making wool shrink-proof should have. The object of the invention is therefore a treatment agent for making wool shrink-proof, which contains compounds suitable for making wool shrink-proof, both in emulsion form and in the form of an organic solution, in which case this property is (should remain intact even after several washes of wool in a washing machine). In particular, it is an object of the invention to find treatment agents in which the active substances do not separate even when left in humid air and are also storage-stable in the form of emulsions over long periods of time.
In this case, the active substances contained in the treatment agent must not have any adverse effects on the so-called wool feel or on the knits and fabrics made from wool. These properties are based on a organopolysiloxane [which has the formula (): R ¹ _o SiO = ... () (in the formula, R ¹ is a methyl group;
Up to 10 mol % of the methyl groups may be replaced by long-chain alkyl or aryl groups, in which case up to 10 mol % of the methyl groups can be replaced by anionic groups bonded to the silicon atom via a carbon atom. unit (aa) of 90 to 99.8 mol% (n has a value of 1.8 to 2.0) and ^the formula (): R ² SiO Alkyl group, mercaptoaryl group, hydrogen _atom , 0 _0.5 ,
or an anionic group bonded to a silicon atom via a carbon atom. may be replaced by an OR ³ - group (in which case R ³ is a lower alkyl group or an elementary atom), and the organopolysiloxane consisting of (aa) and (ab) is The condition that the siloxane has at least one anionic group and 10 to 500 Si atoms per anionic group must be satisfied] 1 to 50% by weight and b Water, 50 to 99 It has been found that a treatment agent consisting of % by weight can be obtained. The processing agent according to the invention furthermore contains customary additives, emulsifiers or organic solvents. Commonly used additives of this type are, for example, flame retardants. In the structural unit (), the group R ¹ is generally a methyl group. However, up to 10 mol% of the methyl groups can be replaced by long-chain alkyl or aryl groups. Examples of such groups are ethyl, propyl, dodecyl or phenyl. Furthermore, up to 10 mol % of the methyl groups can additionally be replaced by anionic groups bonded to the silicon atoms via carbon atoms. This anionic group is bonded to the silicon atom via a divalent hydrocarbon group.
The carbon chain of the divalent hydrocarbon group may be interrupted by oxygen, nitrogen or sulfur atoms. The anionic group is particularly the group -R ⁴ O _n SO ^- ₃ ,

[Formula] or -R ⁴ COO ^- (in this case, m is 0 or 1 and X is an -O ^- group or a group -OR ³ ) falls under this category. This anionic group may be present in the free acid form or may be wholly or partially neutralized. The preparation of silicon-organic compounds modified with anionic groups is known to those skilled in the art. Thus, for example, the group -R ⁴ O _n SO ^- ₃ preferably has the formula: into an organopolysiloxane by reacting a sulfuric acid ester of a silicon organic alcohol represented by be introduced. However, the dialkoxysilanes obtained in this way and modified with sulfatopropyl groups by reacting sulfuric esters with organic alcohols can also be cocondensed with siloxaneols in various ways, for example also in aqueous media. base

[Formula] is, for example, according to British Patent No. 844421

Obtained by the reaction of [Formula] with H ₃ PO ₄ . The anionic group of the formula -R ⁴ COO ^- can be prepared in a known manner, for example by saponification of ≡Si-R ⁴ -CH or by the method described in German Patent Specification No. 1165028 in the presence of a suitable platinum compound. by hydrosilylation of an unsaturated carboxylic acid, such as undecylenic acid. In the structural unit of formula (), the index n is 1.8~
It has a value of 2.0. Structural unit ( ): R ² SiO〓 In R ² represents an alkyl group, a mercaptoalkyl group or a mercaptoaryl group. R ² may be a hydrogen atom or O ₀ . ₅ depending on the proportion
Alternatively, it may be an anion group bonded to a silicon atom via a carbon atom. If multiple units of formula () are present, R ² in the individual units can have the various meanings mentioned above. Methyl is preferably used as the alkyl group in this case as well. Examples of alkyl and mercaptoalkyl or mercaptoaryl groups are methyl, ethyl, mercaptomethyl, 2-mercaptoethyl, 3-mercaptopropyl or 4-mercaptophenyl. Instead of polysiloxanes containing mercaptoalkyl or mercaptoaryl groups, it is also possible to use polysiloxanes which convert into mercaptoalkyl or mercaptoaryl groups in the treatment agent. Examples of such mercapto conjugates are suitable isothiuronium compounds: or sodium ethyl thiosulfate group If this first step of the treatment agent does not completely transform the corresponding mercaptoalkyl/mercaptoaryl compound, the remaining transformation takes place on the fiber. The highest bonded to Si in the structural unit of formula ()
If up to 10 mol % of the oxygen atoms are replaced in each case by two OR ³ groups (in which case R ³ is a lower alkyl group and/or a hydrogen atom), this group
It reacts in water or in humid air with separation of the R ³ OH to give compounds with oxygen atoms that condense two silicon atoms with each other instead of the two OR ³ groups in each case. The siloxane contained in the treatment agent must meet the minimum requirements that it has at least one anionic group and contains from 10 to 500 Si atoms per anionic group. Such siloxanes containing 10 to 200 Si atoms per anionic group are preferably used. Furthermore, polysiloxanes which are composed of 95 to 99.8 mol % of units (aa) and 0.2 to 5 mol % of units (ab) are preferably contained in the formulation. Preference is also given to polysiloxanes in which R ² has the meaning of a mercaptoalkyl group and all anionic groups are bonded to the unit (aa). Preference is given to organopolysiloxanes containing blocks of structural units and units, although they may be distributed statistically within the molecule. The organopolysiloxane contained in the treatment agent according to the invention can, for example, have the following structure: To prepare the treatment agent, in particular sulfate esters of silicon organic alcohols (for example, as described in German Patent No. 1445363) and α,
Synthesized by reaction with ω-polydimethylsiloxane and subsequent cocondensation with γ-mercaptoalkyltrialkoxysilane and/or γ-mercaptoalkylalkyldialkoxysilane and/or alkyltrialkoxysilane. Such organopolysiloxanes are advantageously used. According to the equation, the reaction can be written as: If the values of j and m are small, the product can be converted into emulsion form by simple stirring into water. Stable aqueous systems can be prepared from organopolysiloxanes of this type which do not emulsify themselves using suitable anionic or nonionic emulsifiers. However, the treatment agent can also be present in the form of an organic solution. Suitable organic solvents are hydrocarbons and chlorinated hydrocarbons, such as toluene, xylol, test benzine or 1,1,1-trichloroethane. However, it is often preferred to use the treatment agent in the form of an aqueous emulsion. From the aqueous treatment agent, the anionic organopolysiloxane can be applied to the wool, which can be present essentially in the form of fibres, yarns, woven or knitted fabrics. but,
It is also possible to immerse the material to be treated in an emulsion or solution and subsequently crush it. Furthermore, the wool treated in this way is dried or the solvent is removed. A particular advantage of this method is that the organopolysiloxane contained in the treatment agent does not have to be fixed or hardened by special heat treatments on the wool fibers. In the treated state, the wool should have an active substance content of 0.3-5%, in particular 0.5-3%. The present invention will be explained in detail with reference to the following examples, but the present invention is not limited thereto. Example 1 Simultaneously from two dropping funnels under stirring into 200 ml of a suitable solvent, e.g. methylene chloride, already present in the reaction vessel, the formula: 29.2g of sulfuric acid ester of silicon organic alcohol
(0.135 mol) and a mixture of 200 g (0.27 mol) α,ω-polydimethylsiloxane diol (j=9.6) and 30.45 g (0.3 mol) triethylamine are added dropwise at room temperature. To better control the reaction, dilute the reaction components with methylene chloride and reduce the volume.
Make it 400ml. After a 2-hour post-stirring step, 3-mercaptopropyltriethoxysilane was added to the reaction product.
4.4 g (0.0185 mol) and 13.59 g (0.076 mol) of methyltriethoxysilane are mixed, heated to 60° C. and stirred for an additional 2 hours. Subsequently, the solvent is removed by one distillation. The reaction product has the formula (): (In this case, j is 9.6, K is 1 and is 1 and is 0.7, and R ² is up to 19.6 mol% HS-
(consisting of ₃ CH ₂ ) groups and up to 80.4 mol% H ₃ C groups)
corresponds to This results in an organopolysiloxane composed of up to 96.67 mol % of units of the formula R ¹ _o SiO〓 and up to 3.33 mol % of units of the formula R ² SiO 〓. In this case, n has a value of 2 and R ¹ is 2.48 mol%
Formula up to: -( _CH2 ) _3OSO3 group and _97.52 mol%
Consists of up to H ₃ C groups. R ² represents the above. In this organopolysiloxane, there are 20.2 Si atoms per anion group. From the reaction product, triethylammonium chloride has to be separated off by further pressure filtration, the active substance content is reduced from 1.0 to 1.0 by stirring in water.
Stable emulsions with 50% can be produced. Example 2 400 ml of methylene chloride, α,
ω-Polydimethylsiloxanediol 200g
(0.076 mol) (j=35.1) and 14.63 g (0.1448 mol) of triethylamine, dissolved in 200 ml of methylene chloride via an addition funnel with stirring: 14.39g of sulfuric acid ester of silicon organic alcohol
(0.066 mol) is mixed. After stirring for 2 hours at room temperature, 4.33 g (0.0182 mol) of 3-mercaptopropyltriethoxysilane are then added and heated to 60 DEG C. Furthermore, after a 2-hour post-stirring step, the solvent is distilled off, and triethylammonium chloride is removed from the reaction product by pressure filtration. The reaction product is expressed by the above formula () (in this case, j is
35.1, k is 7 and l is 1.93, corresponding to R ² consisting of up to 100 mol % of HS-(CH ₂ ) ₃ groups. This results in an organopolysiloxane composed of up to 99.34 mol % of units of the formula: R ¹ _o SiO〓〓 and up to 0.66 mol % of units of the formula: R ² SiO〓. In this case, n has a value of 2 and R ¹ is 1.22 mol%
Formula up to: - _{( CH2} ) _3OSO3 and up to 98.78 mol% of _H3C groups. R ² represents the above. In this organopolysiloxane, 1
The number of Si atoms for each anion group is 41.1. The addition of i-propanol to the reaction product improves the dispersibility and makes it possible to produce stable emulsions with a siloxane content of 1.0 to 50% by simply stirring in water. Example 3 In the same manner as in Example 2, 200 g (0.0176 mol) of α,ω-polydimethylsiloxane diol (j = 153), 2.58 (0.0255 mol) of triethylamine were placed in a suitable reaction vessel.
The formula: 2.54g of sulfuric acid ester of silicon organic alcohol
(0.0117 mol) is mixed. After a 2 hour stirring step at room temperature, 4.29 g (0.018 mol) of 3-mercaptopropyltriethoxysilane was added to the solution;
Heat to 60° C. and stir at this temperature for a further 2 hours. Subsequently, the solvent is evaporated off and the triethylammonium chloride is removed by pressure filtration. The reaction product is expressed by the above formula () (in this case, j is
153, K is 2 and l is 3.07, R ² is 100 mol%
(composed of _three HS−(CH ₂ ) groups). This results in an organopolysiloxane composed of up to 99.34 mol % of units of the formula: R ¹ _o SiO〓〓 and up to 0.66 mol % of units of the formula: R ² SiO〓. In this case, n has a value of 2 and R ¹ is 0.22 mol%
Formula up to: -(CH ₂ ) ₃ OSO ₃ groups and up to 99.78 mol % of H ₃ C groups. In this organopolysiloxane, Si for one anion group is
The number of atoms is 230.5. Stable aqueous emulsions with an active substance content of 1.0 to 50% can be prepared from the reaction product in a known manner using suitable emulsifiers, such as, for example, nonylphenol ethylene oxide adduct. Example 4 A reaction vessel is charged with 360 g of water and 3.0 g of dodecylbenzenesulfonic acid and heated to 95° C. while stirring. By the way, in order to produce an organopolysiloxane preparation, 167.0 g (0.56 mol) of octamethylcyclotetrasiloxane was added dropwise to the emulsifier solution through a dropping funnel and stirred vigorously for 60 minutes. The α,ω-polydimethylsiloxanediol in the emulsion, formed in situ, is then formed with the formula: 5.61g (0.015mol) of silane and again
Let stir for 30 minutes. Next, 2.95 g (0.015 mol) of 3-mercaptopropyltrimethoxysilane is added. After a further 20 minute post-stirring step, the emulsion is cooled to 40° C. and the acid contained is neutralized by addition of 11 g of 1 molar potash solution. In this way, an aqueous organopolysiloxane treatment agent having a composition of 99.33 mol % of units of the formula R ¹ _o SiO〓 and 0.67 mol % of units of the formula R ² SiO 〓 is obtained. In the unit of the formula: R ¹ _o SiO〓〓, R ¹ consists of 0.335 mol % of groups of the formula: -(CH ₂ ) ₃ OSO ₃ and 99.665 mol % of H ₃ C groups, and n has a value of 2 . In the unit of formula: R ² Si〓, R ² consists of up to 100 mol % of HS-(CH ₂ ) ₃ groups. The number of Si atoms per anion group is 149.3. Example 5 (Comparative example corresponding to West German Patent Application No. 2365977) The following compounds were mixed: 90 parts by weight of polydimethylsiloxane (3000 cSt.) having a terminal ≡Si-OH- group and a molecular weight of 45000 (CH ₃ O) ₃ Si(CH ₂ ) ₃ NH(CH ₂ ) ₂ NH ₂ 5 parts by weight Partial condensate of H ₃ CSi(OCH ₃ ) ₃ 5 parts by weight Toluene was added in the required amount to produce an impregnating solution from this mixture. and dilute to the desired working concentration. Example of use Pure woolen knitted fabric material is treated with the treatment agents described in Examples 1 to 5 in such a way that after brief drying of the foulard-impregnated knitted fabric a solid deposit of 1% is obtained. The pure wool material was finished with the treatment agent from Example 1 by the leaching method in a laboratory spooler tank, with application with foulard. At a bath pH of 4.5, the active substance is wool.
100% covered. After drying, the active substance deposit was again 1%, based on the amount of pure wool material used. After 24 hours of storage at 20°C, the finished and untreated materials were washed with Perox - needle soap 5g/5g/needle soap at 40°C in a household washing machine.
1 and 2 g/l of sodium carbonate and the laundry is dried in a tumbler. To 20 minutes
The felt surface shrinkage rate was measured after washing 10 times. The felt surface shrinkage rate is calculated by the following formula: Felt surface shrinkage rate = L% + B% - L%・B%/10
0 L% = length shrinkage in percentage B% = width shrinkage in percentage The following values were measured: Untreated material 44% Example 1, padding method 1.8% Example 1, leaching method 2.0% Example 2, padding Example 3, padding method 2.5% Example 4, padding method 3.0% Example 5, padding method 5.0% Unlike the treated material, the unfinished sample exhibited a strongly felted surface. Furthermore,
The post-wash feel of the treated samples is significantly softer than the post-wash feel of the untreated material and corresponds to the pre-wash feel.

Claims (1)

[Scope of Claims] 1a Organopolysiloxane [This has the formula: R ¹ _o SiO] (wherein R ¹ is a methyl group, and up to 10 mol% of this methyl group is a long-chain alkyl group or may be replaced by aryl groups and up to 10 mol % of the methyl groups may be replaced by anionic groups bonded to the silicon atom via a carbon atom, n having a value of 1.8 to 2.0 ) Unit (aa) 90 to 99.8 mol% and formula: R ² Sio〓 (wherein R ² is an alkyl group, a mercaptoalkyl group, a mercaptoaryl group, a hydrogen atom,
O ₀ . ₅ , or an anionic group bonded to a silicon atom via a carbon atom) (ab)
0.2 to 10 mol %, in which case up to 10 mol % of the oxygen atoms bonded to Si may each be replaced by two OR ³ groups, in which case R ³
is a lower alkyl group or a hydrogen atom, and furthermore, the organopolysiloxane consisting of (aa) and (ab) has at least one anionic group and one
The wool must satisfy the condition of containing 10 to 500 Si atoms per anionic group] 1 to 50% by weight and 50 to 99% by weight of water. A processing agent for 2. The processing agent according to claim 1, wherein the coefficient n is 2 in the siloxane unit (aa). 3 The anionic group contained in the siloxane unit (aa) or (ab) is a group -R ⁴ O _n SO ^- ₃ ,
[Formula] or -R ⁴ COO ^- (in which case m is 0 or 1 and X is an -O ^- group or is present in acid form or is wholly or partially neutralized) ^-OR3 , ^R4 is an oxygen atom,
The processing agent according to claim 1 or 2, which is a divalent hydrocarbon group which may be interrupted by a nitrogen atom or a sulfur atom. 4. Any of claims 1 to 3, in which the organopolysiloxane consisting of units (aa) and (ab) contains 10 to 200 Si atoms per anion group. The treatment agent according to item 1. 5 Unit (aa) 95-99.8 mol% and unit (ab)
The processing agent according to any one of claims 1 to 4, comprising 0.2 to 5 mol%. 6. The processing agent according to any one of claims 1 to 5, wherein ^R2 represents a mercaptoalkyl group, and all anion groups are bonded to the unit (aa). 7. The processing agent according to claim 1, further comprising a commonly used additive, an emulsifier or an organic solvent.